JP2000248168A - Flame-retardant and curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a halogen free and curable resin composition having sufficient flame retardancy by compounding a specific amount of an epoxy retaining a phosphorus atom in a moleclue by conjugated bonds into a polyphenylene ether series resin. SOLUTION: This flame-retardant and curable resin composition comprises, per 100 pts.wt. of the sum of (A) a polyphenylene ether series resin and (B) an epoxy retaining a phosphorus atom in a moleclue by conjugated bonds, the component (B) in 0.5-30 pts.wt. as the phosphorus atom. The component (A) is preferably compounded 0.5-30 pts.wt. per 100 pts.wt. of the sum of the component (A) and (B). As the component (B) is used an epoxy group-containing phosphorus compound in which the epoxy group and the phosphorus atom are held together through the conjugated bonds or a phosphorus-containing epoxy resin being held together with the phosphorus atom by the conjugated bonds at a main chain, a side chain, or a terminal. The component (A) and (B) can be used together with a curing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a halogen-free curable resin composition and a cured product obtained by curing the same. Further, the present invention relates to a curable composite material comprising the resin composition and a substrate, a cured product thereof, a laminate comprising the cured product (cured composite material) and a metal foil, and a copper foil with resin.

[0002] The halogen-free resin composition of the present invention exhibits excellent chemical resistance, dielectric properties, heat resistance, and flame retardancy after curing, and is used in the fields of electric industry, space and aircraft industry, etc. , Heat-resistant materials, structural materials and the like. In particular, it can be used as a single-sided, double-sided, multilayer printed board, flexible printed board, build-up board, or the like.

[0003]

2. Description of the Related Art In recent years, there has been a remarkable trend toward miniaturization and high-density mounting methods in the field of electronic devices for communication, consumer use, industrial use, and the like, and accordingly, materials have become more excellent. Heat resistance, dimensional stability, and electrical properties are being demanded. For example, as a printed wiring board, a copper-clad laminate made of a thermosetting resin such as a phenol resin or an epoxy resin has been used. Although these have various performances in a well-balanced manner, they have a drawback that electrical characteristics, particularly, dielectric characteristics in a high frequency range are poor. As a new material for solving this problem, polyphenylene ether has recently attracted attention, and application to copper-clad laminates has been attempted.

For example, Japanese Unexamined Patent Publication (Kokai) No. 61-287739 discloses a laminated plate obtained by curing a resin composition containing polyphenylene ether and triallyl isocyanurate and / or triallyl cyanurate.
No. 7567 discloses a curable resin composition containing a polyphenylene ether modified by reaction with an unsaturated carboxylic acid or an acid anhydride and triallyl isocyanurate and / or triallyl cyanurate, and a laminate obtained using the same. Are disclosed in JP-A-64-69628 and JP-A-64-69628.
No. 69629, JP-A No. 1-113425, 1-11
No. 3426 discloses a curable resin composition containing a polyphenylene ether containing a triple bond or a double bond and triallyl isocyanurate and / or triallyl cyanurate.

Further, as a material obtained by combining polyphenylene ether and epoxy, for example, Japanese Patent Publication No. 64-322
JP-A-2-13521 discloses a curable resin composition containing polyphenylene ether, various epoxy resins such as bisphenol A type epoxy resin and novolak type epoxy resin, and various curing agents such as phenols and amines.
Japanese Patent Application Laid-Open No. 2-166115 discloses a curable resin composition comprising a polyphenylene ether modified by a reaction with an unsaturated carboxylic acid or an acid anhydride, a polyepoxy compound, and a curing catalyst for epoxy. A curable resin composition comprising a processed polyphenylene ether, a polyepoxy compound, and a curing catalyst for epoxy is disclosed.

The above composition is used for various electronic materials such as a copper-clad laminate. In this case, the flame retardancy of the resin is an essential property from the viewpoint of product safety. Heretofore, organic halogen compounds such as aromatic bromides and brominated epoxies have been used as a method for making resins flame-retardant. However, organohalogen compounds can generate highly toxic dioxins during combustion, and their use has recently been limited. In order to cope with such a situation, attempts have been made to impart halogen-free resin with flame retardancy. Until now, however, it has been difficult to provide halogen-free resin with sufficient flame retardancy. It was difficult.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and has a composition containing no halogen, that is, a curable composition which is halogen-free and has sufficient flame retardancy. The present invention provides a resin composition.

[0008]

SUMMARY OF THE INVENTION The present invention firstly comprises: A)
A curable resin composition comprising: a polyphenylene ether-based resin; and (B) an epoxy that retains a phosphorus atom in a molecule by a covalent bond, wherein the phosphorus atom has a component (A) and a component (B). For a total of 100 parts by weight of the components,
A curable resin composition characterized by being contained in the range of 0.5 to 30 parts by weight.

Second, a cured product obtained by curing the first curable resin composition is provided. Third, there is provided a curable composite material comprising a first curable resin composition and a substrate, wherein the curable composite material contains the substrate in a ratio of 5 to 90% by weight. . Fourth, a cured composite material obtained by curing the third curable composite material is provided.

Fifth, a laminate comprising a fourth cured composite material and a metal foil is provided. Sixth, there is provided a metal foil with resin, wherein the film of the first curable resin composition is formed on one surface of the metal foil. Hereinafter, the present invention will be described in more detail. Preferred examples of the (A) polyphenylene ether resin used in the present invention include poly (2,6-dimethyl-1,1) obtained by homopolymerization of 2,6-dimethylphenol.
4-phenylene ether), poly (2,6-dimethyl-
1,4-phenylene ether) styrene graft copolymer, 2,6-dimethylphenol and 2,3,6-trimethylphenol copolymer, 2,6-dimethylphenol and 2-methyl-6-phenylphenol Copolymers, polyfunctional polyphenylene ether resins obtained by polymerization in the presence of 2,6-dimethylphenol and a polyfunctional phenol compound, such as those disclosed in JP-A-63-301222 and JP-A-1-297428. And copolymers containing units of general formulas (A) and (B) as described above.

With respect to the molecular weight of the polyphenylene ether-based resin described above, the viscosity number ηsp / C measured with a 0.5 g / dl chloroform solution at 30 ° C. is 0.1 to 1.
Those in the range of 0 can be preferably used. Further, the polyphenylene ether-based resin referred to in the present invention includes a modified product. Such a modified product is specifically a polyphenylene ether resin containing an unsaturated group (Japanese Patent Application Laid-Open No. 64-69).
No. 628, JP-A-1-113425, JP-A-1-11
No. 3426), and a reaction product of a polyphenylene ether resin with an unsaturated carboxylic acid and / or acid anhydride.

In the present invention, the polyphenylene ether-based resin (A) is preferably blended in an amount of 10 to 80 parts by weight based on 100 parts by weight of [(A) + (B)]. The epoxy (B) used in the present invention that retains a phosphorus atom in a molecule by a covalent bond (hereinafter referred to as “phosphorus-modified epoxy”)
Can be used as an epoxy group-containing phosphorus compound in which an epoxy group and a phosphorus atom are connected via a covalent bond, or a covalent bond to a phosphorus atom in the main chain, side chain or terminal. A phosphorus-containing epoxy resin, for example, as described in JP-A-2-269730,
No. 59018, Tokuhyo Hei 8-503004, 8-50
No. 7811, No. 8-507812, No. 8-50781
No. 3, 8-507814, 10-503540, etc., phosphinic acid, phosphonic acid,
Pyrophosphonic acid and phosphonic acid hemiester, phosphoric acid,
Examples include phosphorus-modified epoxies derived from at least one compound selected from the group consisting of phosphorous acid and phosphine oxide.

The above epoxy group-containing phosphorus compound has, for example, a reaction between glycidol and an acid chloride such as phosphonic chloride and phosphoric acid chloride, a reaction between epichlorohydrin and phosphonic acid and phosphoric acid, and an olefin double bond. It can be synthesized by an epoxidation reaction of a phosphorus compound containing a group. About the thing which can be used as an epoxy group containing phosphorus compound, when a specific name is shown, for example, methyl diglycidyl phosphonate, butyl diglycidyl phosphonate, vinyl diglycidyl phosphonate, phenyl diglycidyl phosphonate, methyl diglycidyl phosphate, n-butyl diglycidyl phosphate , Isobutyl diglycidyl phosphate, allyl diglycidyl phosphate, phenyl diglycidyl phosphate, p
-Methoxyphenyl diglycidyl phosphate, p-isopropyloxyphenyl diglycidyl phosphate,
Femilthiodiglycidyl phosphate, triglycidyl phosphate, tris (glycidylethyl) phosphate, p-glycidylphenylethylglycidyl phosphate and the like can be mentioned.

The phosphorus-containing epoxy resin can be synthesized by, for example, reacting a polyepoxy compound with an acid anhydride such as phosphonic anhydride / phosphinic anhydride. Such acid anhydrides include phosphinic anhydrides such as dimethylphosphinic anhydride, ethylphenylphosphinic anhydride, and diphenylphosphinic anhydride, methane-1,1-bis-methylphosphinic anhydride, and butane-1,4-bisanhydride. Alkane-bis-phosphinic acid such as -methylphosphinic acid, methanephosphonic anhydride, propanephosphonic anhydride, benzolphosphonic anhydride and the like are preferably used. At this time, by controlling the reaction conditions such as the ratio of the acid anhydride added to the polyepoxy compound, the temperature, and the solvent used, the phosphorus atom content in the phosphorus-containing epoxy resin is 0.1 to 50% by weight. Can be set to any value in the range.

As the polyepoxy compound, any compound having two or more epoxy groups in one molecule may be used, and known compounds may be used alone or in combination of two or more. Representative examples include glycidyl ether type epoxy resins obtained by reacting phenols or alcohols with epichlorohydrin, glycidyl type epoxy resins obtained by reacting amines or cyanuric acid with epichlorohydrin, Examples thereof include an internal epoxy resin obtained by oxidation of a double bond (for details, refer to “Epoxy Resin Handbook”, edited by Masaki Shinbo, Nikkan Kogyo Shimbun, 1987).

The (A) polyphenylene ether-based resin and (B) the phosphorus-modified epoxy can be used together with a curing agent. As such a curing agent, dicyandiamide, aromatic amine and the like are usually used for curing an epoxy resin, and phenol novolak resin, cresol novolak resin, bisphenol A type resin and aniline are used as a phenol curing system. Denaturation
Nitrogen-modified phenolic resins such as melamine-modified, guanidine-modified, and polyamide-modified may be used, and these may be used alone or in combination of two or more. Further, as a curing agent, a crosslinkable compound such as diallyl phthalate, divinylbenzene, a polyfunctional acryloyl compound, a polyfunctional methacryloyl compound, a polyfunctional isocyanate, an unsaturated polyester, triallyl isocyanurate, triallyl cyanurate, polybutadiene, styrene -Butadiene, styrene-butadiene-styrene, and the like, and these can be used alone or in combination of two or more. It is also possible to use a mixture of two or more compounds which are usually used for curing an epoxy resin and a crosslinkable compound.

A curing accelerator may be used together with a curing agent for the (A) polyphenylene ether-based resin and (B) the phosphorus-modified epoxy, and as such a curing accelerator, a curing accelerator usually used for an epoxy resin may be used. The former includes, for example, an imidazole compound, and the latter, for example, a normal peroxide such as perhexin 25B.

The halogen-free curable resin composition of the present invention can be used by blending the above polyepoxy compound in addition to the above components (A) and (B). Also,
For the purpose of imparting desired performance according to the application, fillers and additives can be blended and used in amounts that do not impair the original properties. Examples of such a filler include carbon black, barium titanate, glass beads, and hollow glass spheres. In addition, examples of the additive include an antioxidant, a heat stabilizer, an antistatic agent, a plasticizer, a pigment, a dye, and a colorant. Further, one or more thermoplastic resins and thermosetting resins other than the component (A) and the component (B) can be blended.

In the present invention, the phosphorus atom content relative to 100 parts by weight of [(A) + (B)] is an important factor, preferably 0.5 to 30 parts by weight, more preferably 3 to 30 parts by weight. To 30 parts by weight, more preferably 13 to 30 parts by weight. If the phosphorus atom content is less than 0.5 parts by weight, it is difficult to achieve flame retardancy, and if it exceeds 30 parts by weight, heat resistance and moisture resistance are reduced, or flame resistance becomes unstable.

As a method of mixing the above components (A) and (B) and other components as required, a solution mixing method for uniformly dissolving or dispersing each component in a solvent, or an extruder or the like is used. A melt blending method performed by heating can be used. As the solvent used for the solution mixing, aromatic solvents such as benzene, toluene, and xylene, and tetrahydrofuran are used alone or in combination of two or more.

The curable resin composition of the present invention may be formed into a desired shape in advance according to its use. The molding method is not particularly limited. Usually, a casting method in which the resin composition is dissolved in the above-described solvent and molded into a desired shape, or a heat melting method in which the resin composition is heated and melted to form a desired shape is used. The cured product of the present invention is obtained by curing the curable resin composition described above. The method of curing is arbitrary, and a method using heat, light, an electron beam, or the like can be employed.

When curing by heating, the temperature is
Depending on the type of radical initiator, 80-30
0 ° C, more preferably in the range of 120 to 250 ° C. The time is about 1 minute to 10 hours, more preferably 1 minute to 5 hours. Further, this cured product can be used by being bonded to a metal foil and / or a metal plate, similarly to a cured composite material described later.

Next, the curable composite material of the present invention and its cured product will be described. The curable composite material of the present invention comprises the curable resin composition of the present invention and a substrate.
As a substrate used in the present invention, a roving cloth,
Liquid crystal fiber such as cloth, chopped mat, surface mat, etc., glass cloth, asbestos cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloth, wholly aromatic polyamide fiber, wholly aromatic polyester fiber and polybenzozar fiber Woven or non-woven fabric obtained from synthetic fibers such as polyvinyl alcohol fiber, polyester fiber, and acrylic fiber, cotton cloth,
Natural fiber cloths such as linen cloth and felt, carbon fiber cloths, kraft paper, cotton paper, and natural cellulosic cloths such as paper-glass mixed paper are used alone or in combination of two or more.

In the present invention, the proportion occupied by the substrate is 5 to 90 parts by weight, preferably 10 to 80 parts by weight, more preferably 20 to 70 parts by weight, based on 100 parts by weight of the curable composite material. If the amount of the base material is less than 5 parts by weight, the dimensional stability and strength after curing of the composite material are insufficient, and if the amount of the base material is more than 90 parts by weight, the dielectric properties of the composite material are unfavorably poor.

In the curable composite material of the present invention, if necessary, a coupling agent can be used for the purpose of improving the adhesion at the interface between the resin and the substrate. As the coupling agent, general ones such as a silane coupling agent, a titanate coupling agent, an aluminum-based coupling agent, and a zircoaluminate coupling agent can be used. As a method for producing the curable composite material of the present invention, for example, the components (A) and (B) of the present invention and other components as necessary may be mixed with the aforementioned aromatic or ketone-based solvent or a mixture thereof. A method of uniformly dissolving or dispersing in a solvent, impregnating the substrate, and then drying is used.

The impregnation is performed by dipping (dipping), coating or the like. The impregnation can be repeated multiple times as necessary, and in this case, the impregnation can be repeated using multiple solutions having different compositions and concentrations to finally adjust the desired resin composition and resin amount It is. The cured composite material of the present invention is obtained by curing the curable composite material thus obtained by a method such as heating. The production method is not particularly limited,
For example, a plurality of the curable composite materials are laminated, and the respective layers are adhered to each other under heat and pressure, and simultaneously thermoset to obtain a cured composite material having a desired thickness. Moreover, it is also possible to obtain a cured composite material having a new layer configuration by combining the cured composite material once cured by adhesion and the curable composite material. Lamination molding and curing are usually performed simultaneously using a hot press or the like, but both may be performed independently. That is, the uncured or semi-cured composite material obtained by lamination molding in advance can be cured by heat treatment or another method.

The molding and curing are performed at a temperature of 80 to 300.
° C, pressure: 0.1 to 1000 kg / cm ² , time: 1 minute to 10 hours, more preferably temperature: 150 to 2
50 ° C., pressure: 1 to 500 kg / cm ² , time: 1 minute to
It can be performed in a range of 5 hours. The laminate of the present invention is composed of the cured composite material of the present invention and a metal foil. Examples of the metal foil used here include a copper foil and an aluminum foil. The thickness is not particularly limited, but is 5 to 200 μm, more preferably 5 to 1 μm.
It is in the range of 05 μm.

The method for producing the laminate of the present invention includes:
For example, the above-described curable composite material and a metal foil and / or
Alternatively, a method of laminating a metal plate in a layer configuration according to the purpose, bonding the respective layers under heat and pressure, and simultaneously performing thermosetting can be used. In the laminate of the present invention, the curable composite material and the metal foil are laminated in an arbitrary layer configuration. The metal foil can be used as both a surface layer and an intermediate layer.
In addition to the above, lamination and curing may be repeated a plurality of times to form a multilayer.

An adhesive can be used for bonding the metal foil. Examples of such an adhesive include, but are not particularly limited to, epoxy-based, acrylic-based, phenol-based, and cyanoacrylate-based adhesives. The above-mentioned lamination molding and curing can be performed under the same conditions as in the case of the curable composite material of the present invention.

Finally, the resin-coated copper foil of the present invention will be described. The resin-added copper foil of the present invention comprises the curable resin composition of the present invention and a metal foil. Examples of the metal foil used here include a copper foil and an aluminum foil. The thickness is not particularly limited,
It is in the range of 200 μm, more preferably 5 to 105 μm.

The method for producing the resin-coated copper foil of the present invention is not particularly limited. For example, the component (A)
A method of uniformly dissolving or dispersing the component (B) and, if necessary, other components in an aromatic or ketone-based solvent or a mixed solvent thereof, applying the mixture to a metal foil, and then drying the mixture. The application can be repeated multiple times as necessary, and in this case, the application can be repeated using multiple solutions with different compositions and concentrations to finally adjust the desired resin composition and resin amount It is.

[0032]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, specific examples of the present invention will be described by way of examples. In the following Examples and Comparative Examples, “parts” means “parts by weight”.

[0033]

Example 1 Poly (2,500) having a viscosity number ηsp / C of 0.54 measured in a chloroform solution of 0.5 g / dl at 30 ° C.
6-dimethyl-1,4-phenylene ether) 100
Phenyldiglycidylphosphonate, 200 parts of epoxidized novolak, and 200 parts of diaminodiphenylmethane were dissolved in toluene to prepare a varnish, and a glass cloth having a basis weight of 107 g / m ² was immersed in the varnish to perform impregnation. The resulting mixture was dried in a curable composite material.

Next, six pieces of the above-mentioned curable composite material are laminated so that the thickness after curing becomes about 0.8 mm, and a copper foil having a thickness of 35 μm is placed on both sides thereof at 180 ° C. and 40 kg / cm.
² were molded and cured using a press molding machine for 90 minutes.
The obtained laminate was subjected to a flammability test based on the UL94 standard, and the result was V-0.

[0035]

Examples 2 to 5 A laminate was prepared in the same manner as in Example 1 except that the number of parts of the curable resin composition was changed as shown in Table 1.
The flammability was measured, and all were set to V-0 according to UL94 standard.

[0036]

EXAMPLE 6 300 parts by weight of epoxidized novolak (epoxy value 0.55) and 20 parts by weight of phosphonic anhydride were added to ethyl methyl ketone, and the mixture was added at room temperature for 60 minutes and then 100 parts by weight.
By refluxing at 90 ° C. for 90 minutes, a phosphonic acid-modified epoxidized novolak having a phosphorus content of 1% by weight was obtained.

Poly (2,2) having a viscosity number ηsp / C of 0.54 measured at 30 ° C. in a 0.5 g / dl chloroform solution.
6-dimethyl-1,4-phenylene ether) 100
, 200 parts of a phosphonic acid-modified epoxidized novolak, 200 parts of a bisphenol A type epoxy, and 200 parts of diaminodiphenylmethane were dissolved in toluene to prepare a varnish, and a glass cloth having a basis weight of 107 g / m ² was immersed in the varnish. And dried in an air oven to obtain a curable composite material.

Next, six pieces of the above-mentioned curable composite material are laminated so that the thickness after curing becomes about 0.8 mm, and a copper foil having a thickness of 35 μm is placed on both surfaces thereof at 180 ° C. and 40 kg / cm.
² were molded and cured using a press molding machine for 90 minutes.
The obtained laminate was subjected to a flammability test based on the UL94 standard, and the result was V-0.

[0039]

Examples 7 to 11 Tables 2 and 3 were used as phosphorus-containing epoxy resins.
A laminate was prepared and the flammability was measured in the same manner as in Example 6 except that the compound shown in No. 3 was synthesized, and all were set to V-0 according to UL94 standard.

[0040]

Example 12 A varnish was prepared in the same manner as in Example 1 and applied to a copper foil having a thickness of 18 μm with a bar coater so that the resin layer had a thickness of 50 μm. A copper foil was produced. Next, two pieces of the resin-attached copper foil are superimposed, and heated at 180 ° C. and 40 kg / cm ² for 9 hours.
It was molded and cured using a press molding machine for 0 minutes.

With respect to the laminate obtained here, UL94
When a flammability test was performed based on the standard, it was V-0. The results of Examples 1 to 12 are summarized in Tables 1 to 3.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

Comparative Example 1 A laminate was prepared and flammability was measured in the same manner as in Example 6 except that the amount of the phosphonic anhydride-modified epoxidized novolak was changed to 42 parts, and the flammability was measured.
Became 1

[0046]

Comparative Examples 2 to 4 A laminate was prepared and flammability was measured in the same manner as in Comparative Example 1 except that the number of parts of the curable resin composition was changed as shown in Table 4, and the results were shown in Table 5 in accordance with UL94 standard. The result was obtained. The results of Comparative Examples 1 to 4 are collectively shown in Table 4.

[0047]

[Table 4]

[0048]

According to the present invention, it is possible to provide a curable resin composition which is halogen-free and has sufficient flame retardancy (for example, V-0 in UL94 test).

Claims (6)

[Claims] (A) a polyphenylene ether-based resin,
And (B) an epoxy that retains a phosphorus atom in the molecule by a covalent bond, wherein the phosphorus atom is contained in the composition by a total of 1 component (A) and 1 component (B).
A curable resin composition characterized by being contained in an amount of 0.5 to 30 parts by weight based on 00 parts by weight. 2. A cured product obtained by curing the curable resin composition according to claim 1. 3. A curable composite material comprising the curable resin composition according to claim 1 and a base material, wherein the base material is contained at a ratio of 5 to 90% by weight. . 4. A cured composite material obtained by curing the curable composite material according to claim 3. 5. A laminate comprising the cured composite material according to claim 4 and a metal foil. 6. A metal foil with resin, wherein the film of the curable resin composition according to claim 1 is formed on one surface of the metal foil.